Process for the polymerization of olefins



Allg' 29 1939i I A. BoUL'BEE `l Filed gun@ .19,1 193s lolsi's3- FOR THE POLYMERIZATION of' oLFINs Patented Ang. 1.939

Pnocnss Fort THE POLYMERIZATION F OLE FINS

Arthur Hallam ou'lthee, Martinez, Calif., assignor to Shell Development Company,

San Francisco, Calif., a corporation of Delaware Application June 19,

6 Claims.

This invention relates to the manufacture of gasoline-type hydrocarbons from cracked hydrocarbon gases containing secondary and tertiary base oleflns by polymerization of these oleflns.

process whereby from normally gaseous hydrocarbons comprising olens, a maximum yield of polymer gasoline of high octane number (A. S. T. M. method D-357-34-T) and lead .s us.

. ,Further advantages of my process are more fully explained hereinafter.

The expression "normally gaseous hydrocarbons comprising olens as herein defined refers to hydrocarbon mixtures comprising hydrocarbons of and less 'carbon atoms. Mixtures to be suitable for my process must consist at least pari tially of 4 and/ or 5 carbon secondary and tertiary base. olefins and may, but need not, contain hydrocarbons of 3 and less carbon atoms, and hydrogen. The normally gaseous` hydrocarbons which are used in my process nlay be byproducts from cracking and/ or reforming of hydrocarbons, or may originate in the dehydrogenation of normally gaseous saturated hydrocarbons or may be produced by dehydration of alcohols or the re- 'nloval' of hydrochloric acid from suitable chlorinated hydrocarbons. Y

The polymerization catalyst is preferably an acid-acting catalyst. Suitable polymerization catalyst, which if solid, may be usedalone or in admixture with each other, or deposited onsolid carriers; or which ifl liquid or gaseous may be contacted or mixed'with the hydrocarbons in any convenient manner or preferably may be used in `the form` of solid complex compounds and/or in- .corporated in solid carriers to form solid catalyst 4| masses, 4are the mineral Oxy-acids, such as the phosphoric and phosphorous' acids .H4P2Os, H4Pa01, HPOsg'HsPaOs, HaPOa, HsPOz) and their anhydrides, as P205, etc.; the acid phosphoric and phosphorous acid salts; the' phosphorus oxy-halides; the sulfuric acids, arsinic acids and the like; the ZnClz, MgCl2, FeCls, NiClz, BeClz, BFs, SnCls', TiCk, PF1, and the like, may be used in the form of organic or inorganic complex pounds BeFn; ASFS.

It is the purpose of this invention to provide a' yields inorganic halides, as AlCla,

which if desired.

in'conjunctinn with subi936,- serial No. 86,122

(ol. rss-1o) stances such as nitrohydrocarbons, carboxylic acids, ethers, or non-catalytic metal halides; the acid-acting salts of. mineral Oxy-acids as ZnSOa,

CdSO4, PbSO4, BOCl,

advantageously employed.4 in conjunction metal, as', for example, zinc, aluminum,

of Group VIII of the tain of these catalysts.

pumice, fullers earth,

clay, bentonite, aluminum .calcined mixture of ceous material, as .kieselguhr, pumice, etc.

To illustrate my process,

panying drawing enter from a source not absorber 2 where they pass absorption oil entering ethane and lighter tions `that 2carbon as well and only through transfer line 5 from reboiler 1 in and are fractionated into Cds (P002, and the like. In. some cases, catalytic agents of thistype are f5 Witha metals periodic table, etc. Also small quantities of hydroxy compounds, such as water', alcohol, etc., may be used to activate cer- 10 The acid and acid-acting catalysts of the type herein described, particularly the phosphorus Oxy-acids, may be advantageouslyemployed as constituents of solid catalyst masses. For examl ple, they may be deposited on; or incorporated with a solid siliceous or similar absorptive material. Suitable absorptive materials are silica gel, kieselguhr, Death Valley hydrosilicate, alumina, metallurgical ook activated charcoal, and the like. Particularly good results may be obtained by employing a solid catalyst mass comprising a a phosphoric acid and a sili- I refer to the accomwhich represents a flow diagram of one possible form of the process. Nornially gaseous hydrocarbons containing olefins shown through line I into in countercurrent to absorber 2 through line 4. A light fraction of gas consisting essentially of is withdrawn through line 3 while 3-carbon hydrocarbons and heavier are, 35 dissolved-in the absorption oil. If desired, the absorber 2 may be operated under such condihydrocarbons are absorbed methane and hydrogen escape through line 3. Fat absorption oil is transferred o to fractionator 8 in which the dissolved hydrocarbons are driven oi by heat the bottom of fractionator 6,

an intermediate fraction consisting essentially of 3-'carbon or 2 and leave the frac-- 8, and a heavierfraction of 4-carbon and heavier-hydrocarbons, which is transferred through line 9 to heat exchanger Il. Lean absorption oil is returned by absorber 2.

ily-passing absorber! pump I I in line l2 through cooler 1f desired, the hydrocarbons ceed directly to heat exchanger' Il andline l to olefin containing gas in heat exchanger I is heated to between about Z50-425 F., after which it is conducted through conduit I5 to treater I6, which treater contains a suitable solid polymerization catalyst mass. During passage through the treater, polymerization of a portion of the olens takesplace, and the polymerized mixture so produced is transferred through transfer line l1 into fractionator I8 where residual gas is separated from polymers, the polymers passing through cooler I9 in line 20 into storage tank`2I and the residual gas, containing a reduced amount of olens is conveyed by pump 23l in laine 22 through heating coil 24 located in furnace The propane-propylene fraction in line 8 orig- I inating in -fractionator G may be combined with the residual gas in line 22 if desired. The gases in coil 26 are heated to above 900 F. and the heated gases then pass through reactor 26, in which time is allowed for the polymerization of olens, to the quenching chamber 21. Quenching may be accomplished by admixing to the hot charge in chamber 2l the polymer gasoline produced in the process and suppliedthrough line 28 in quantities suiilcient to lower the temperature of the resulting mixture to below about 800 F. The quenched mixture then passes through line 21 and heat exchanger I0 in indirect heat exchange relation against the incoming fresh feed, and then continues through line 29 into fractionator 30, where tar and polymers heavier than gasoline are separated from gasoline type and lighter hydrocarbons. Heavy polymers leave fractionator 30 through bottom line 3 I and gasoline and lighter hydrocarbons proceed throughV transfer line 32 to fractionator 33. In the latter, gasoline is separated from residue gas, the gasoline going through cooler 34 in line 35 to polymer tank 3.6, a portion of the gasoline being diverted by pump 3l in line 28 to quenching chamber 2l. The residue gas is withdrawn Afrom fractionator 33 through line 38 and is combined withgas from the absorber 2 in line 3, the mixture to be discharged as waste gas. If desired, the residue gas in line 33 may be returned to the absorber 2 through line 39, or a portion thereof may be recycled through line 40 to join the residue gas from the catalytic polymerization step in line 22.

Normally gaseous olens comprise ethylene, propylene, secondary and tertiary base butylenes and occasionally secondary and tertiary base amylenes. If the catalytic polymerization in the presence of a suitable solid polymerization catalyst is conducted under such conditions as to effect a selective polymerization of tertiary base olens in preference to the remaining olens, a gasoline is obtained which, particularly after hydrogenation, has a higher octane number and greater lead susceptibility than a similar gasoline Dlfoduced under non-selective conditions.

To facilitate preferential polymerization of the tertiary base olens, I usually begin by fractionating the olef'lns containing hydrocarbon gas to produce a fraction consisting essentially of hydrocarbons of four and more carbon atoms, which fraction I call for convenience the BB fraction (butane-butylene fraction) and which is a' tertiary base olen concentrate, ,containing substantially all of the oleflns of four and more carbon atoms originally contained in the gas, and a lighter fraction comprising `the hydrocarbons of less than four carbon atoms. The fractionation may be carried out in any conventional manner: such as distilling under pressure at low temperature and, if desired, inthe presence of an absorption oil.

Tertiary base oleflns are generally known to be more reactive than secondary `base olei'lns and ethylene, ethylene being the only primary base olen known. Tertiary base olefins therefore tend to be polymerized in preference to nontertiary base olens under a wide range of conditions. Due tothe fact, however, that hydrocarbon gases of thetype obtained by cracking,

'Iime and particularly temperature of contact with a catalyst of a given activity are the most important factors aifecting polymerization. At an elevated temperature up to about 600 F. the rate of polymerization in the presence of acidacting catalysts of the type hereinbefore described rises with increasing temperature, and with the lengthening of the timev of contact'the degree of "polymerization increases. For every temperature below 600 F. there is a corresponding optimum time, which yields the largest amount of gasoline hydrocarbons, the optimum time-temperature combination in turn depending on the activity of the catalyst and the composition of. the hydrocarbon gas. For the sake of good selectivity'I control the time-temperature conditions so as to produce an amount of gasoline less than the maximum. While normally the optimum polymerization temperature in the presence of acid-active catalysts particularly of the phosphoric acid type hereinbefore described is about 450 F. or higher, I prefer to operate at a temperature between about 3D0-425 F. and preferably below 400 F., limiting the time of contact so that the ratio of tertiary base oleln to total olens polymerized is not lower than about .5. Variations in pressure except insofar as they affect the time of contact fora given throughput appear to have little inuence on the selectivity.

The effect of the preferential polymerization of isobutylene on the octane number of gasolines is well illustrated by the following examples, in which a BB fraction containing 30% normal butylene and 20% isobutylene was polymerized at a pressure of 600 lbs. per sq. in. by contacting with a fresh catalyst mass in which the active ingredient was a phosphoric acid.

In the table below, percent total olens polymerized, ratios of isobutylene to normal butylene polymerized, and octane numbersof the hydrogenated polymer gasolines are compared for various throughputs at various temperatures.' The throughputs isexpressed in gallons liquied BB fraction per pound of catalyst per hour.

From the above examples it appears that polymerization at a temperature of about 350 F.

lower, and at lower at abOllt 350 erally not exceeding 400 about 1100 F., if desired pressureunder conditions which are known togve highest yields of gasoline-type' hydrocarbons yields a relatively high percentage of a very high octanev number gasoline. At temperatures above 375 F. the octane number for a given yield is temperatures although 'even higher octane number gasoline may be produced, the yields drop off sharply. Therefore, I usually prefer to carry out the catalytic polymerization F. to 375 F. as long as the catalyst is relatively active. Upon use, the activity of the catalyst declines, and the temperature optimum then may shift toward higher temperatures, in

which case I may gradually increase the poly- 1 merization temperature up to temperatures genor 445 F., in order to counteract Ithis decline in catalysts activity.

Since in accordance with the above, only part of the oleflns are polymerized, the residue gas from the selective polymerization of my process contains a considerable amount of olens, which in the case of the BB fraction, consist chiefly of secondary base butylene and perhaps amylene.

In order to convert these olefins to gasoline, I now subject the residue gas to a thermal polymerizaton prooessin the absence of a catalyst at a temperature above 900 F. and preferably above under superatmospheric from normally gaseous oleiins. If fractionation of the hydrocarbon gas in the manner hereinbefore described has preceded the catalytic polymerization, I may combine part or all of the untreated fraction with the residual gas from the catalytic polymerizatons, so as to produce a mixture which may contain ethane, propylene, secondary base butylene, and secondaryV base amylene, which mixture I polymerize thermally, as described, in the absence of a catalyst.

During' the thermal polymerization some polymers heavier than gasoline and tar are formed. I have observed that the amount of these higher polymers is considerably reduced if catalytic polymerization precedes the thermal polymerization. This reduction of undesirable products is probably due to the almost complete elimination of the more reactive tertiary base oleflns which have a tendency to form higher polymers at the elevated thermal polymerizing temperatures. y

A comparison of the quantities and qualities -of the gasolines produced by the catalytic, thermal and combination processes reveals that by the catalytic polymerization not more than about 90% of the total verted to gasoline genation, has an A. S. T. M. octane number of about 9 0 .and a high` lead susceptibility. In

oleflns in the gas can be conthe thermal treating process gasoline yields in' and up to 150% of the olen gas are obtainable, the gasoline excess of 100% content of the havingan A. S. T. M. octane numbervarying from about 'l5 to 95, dependingupon the 4temperature and pressures of the treatment. lAt relatively high temperatures higher octane number -gasolinas are produced, .which are largely aromatic in character. Such gasolines have very lowl lead susceptibility, 'which in extreme cases may approach zero. If it is attempted to hydrogenate them for the purpose otimproving lead susceptibility, octane numbers are greatly reduced because of conversion of aromatic to naphthemc hydrocarbons. In consequence, thermally produced gasolines are useful only for the4 blending of -gasolines which require octaneI numbers below about which gasoline, after hydro-I 90, while catalytically ,manuwhich can be produced by catalytic polymerization. About one-half ofl this amount yof gasoline has an octane rating and lead susceptibility which. is higher than that of a gasoline produced by the catalytic treatment conducted under conditions of maximum gasoline yield, or by thermal polymerization, while the other half has the properties of an ordinary thermal polymer gasoline.

If an amount of olefin containing hydrocarbon gas is divided into two. portions and each portion is polymerized separately, one catalytically and the other one thermally, to produce two gasolines, the total yield thereof is smaller and the octane number and lead susceptibility of a blend 'of the two is lower, than if the same amount of cracked gas had been treated and polymerized by my combination process.

Depending on the nature of the catalyst used in the catalytic polymerization, the catalytically treated reaction mixture may or may not contain free mineral acid which is apt to cause serious corrosion in fractionators and other pieces of equipment through which the polymer gasoline and/or the unreacted residual gas must pass subsequently. Therefore if the catalytically treated unreacted mixture does contain corrosive acids the mixture is preferably neutralized in any convenient manner, such as by injecting ammonia, passing the mixture through solid or aqueous caustic or the like, treating with alkali suspended in oil, etc., prior to fractionating it and thermally polymerizing the residual gas as described.

I claim as my invention:

1.1n the process of polymerizing normally gaseous hydrocarbons of the type produced vin cracking, comprising tertiary base and non-ter- Atiary 'base olefins, thereby producing a polymer,

separating the polymer from the unreacted ole- -fins containing fraction, combining the latter with the said middle fraction, subjecting the re,

sulting mixture to a `thermal non-catalytic polymerization at a thermal perature to produce additional polymers, seppolymerization temarating same from residual gaseous hydrocarbons, and returning the latter to the said fracltionating zone. 2.1In` the process of polymerizlng normally gaseous hydrocarbons of the type produced in cracking,

tertiary base olefins to produce gasoline-type motor fuel, the steps of fractionating said hydro- 'Il r comprising tertiary base and noncarbons in a fractionating zone to produce a light fraction consisting essentially of methane --three carbon and lighter hydrocarbons comprising tertiary base and non-tertiary base olens,

contacting said heavy fraction with a polymerization catalyst capable of converting normally gaseous olens to gasoline-type hydrocarbons, at an elevated temperature under conditions to polymerize predominantly thetertiary base' oleflns while only Ipartially polymerizing the less reactive non-tertiary base olens, thereby' producing a polymer, separating the polymer from the unreacted olens containing fraction, combining the latter with the said middle fraction, subjecting the resulting mixture to a noncontains a. phosphoric aci catalytic thermal polymerization t a thema! polymerization temperature to produce additional polymers, separating same from thelresidual gaseous hydrocarbons, and vreturning the latter to the said fraotionating zone.

3. The process of claim 1 in which the catalytic polymerization is carried out at a temperature below about 425 F.

4. The process of claim 1 in which the catalytic polymerization is carried out ata temperature between 300 and 425 F. A

5. The process of claim 1in which the catalyst 'as its activeingredient.

6. The process of claim 1 in which the thermal polymerization temperature is above 1 100" 'I'. 

